CN102387856B - Subregion catalyst for diesel fuel applications - Google Patents

Subregion catalyst for diesel fuel applications Download PDF

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Publication number
CN102387856B
CN102387856B CN201080014918.1A CN201080014918A CN102387856B CN 102387856 B CN102387856 B CN 102387856B CN 201080014918 A CN201080014918 A CN 201080014918A CN 102387856 B CN102387856 B CN 102387856B
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washcoat
district
oxidation catalyst
catalyst
platinum
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CN102387856A (en
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J·B·霍克
J·C·德特兰
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BASF SE
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BASF SE
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    • B01J35/19—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/103—Oxidation catalysts for HC and CO only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0682—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Abstract

Disclosing such as makes the unburned hydrocarbon (HC) of Diesel engine and advanced burning diesel oil engine emission and carbon monoxide (CO) aoxidize and make nitrogen oxides (NO for processing advanced combustion engine exhaust emissionx) reduce oxidation catalyst compound, method and system.More particularly, disclosed the washcoat complex comprising at least two washcoat, wherein the first washcoat comprises palladium component, and the second washcoat contains platinum, and at least about the 50% of platinum total amount is positioned at catalyst rear portion.

Description

Subregion catalyst for diesel fuel applications
The cross reference of related application
According to 35USC § 119 (e), application claims enjoy the 61/167th, No. 575 U.S. Provisional Application preferential only, it is incorporated herein by.
Technical field
Embodiment of the present invention relate to the oxidation catalyst of split plot design.More specifically, embodiment relates to the subregion catalyst formulation comprising Pt and the Pd in refractory metal oxides load (such as containing Ce load), and reduces the purposes of the carbon monoxide in Diesel engine and advance combustion diesel engine system and hydrocarbon.
Background technology
The user that operates to of lean combustion engine (such as Diesel engine and lean burn petrol engine) has saved fuel, and owing to it runs with high air/fuel ratio when fuel is thin, compared with spark ignition stoichiometric gasoline electromotor (spark-ignitedstoichiometricgasolineengine), the gaseous hydrocarbon of its discharge and carbon monoxide are significantly less.The emission of Diesel engine includes particulate matter (PM), nitrogen oxides (NOx), unburned hydrocarbon (HC) and carbon monoxide (CO).NOxIt is the term of nitrogen oxides for describing multiple chemical type, including nitric oxide (NO) and nitrogen dioxide (NO2)。
A lot of difference is there is between diesel engine exhaust and the antigravity system of gasoline engine exhaust for processing.A significant difference between both engine types and its operation is petrol engine is spark ignition type and operation in chemically correct fuel, and Diesel engine is compression ignition engine, and it runs under the large excess of condition of air.The emission of the electromotor of both types is very different and needs diverse catalyst scheme.Owing to Diesel engine being formed substantial amounts of NOxAnd particle emission, processing of usual diesel engine emissions is more increasingly complex than the process of gasoline engine emissions thing.
Two key components of exhaust gas particle material are soluble organic fraction (SOF) and flue dust composition (soot filter).SOF condenses stratification on flue dust, and it derives from unburned diesel fuel and lubricating oil.Temperature according to waste gas, SOF can exist with gaseous state or liquid (droplet of liquid condensate) in diesel exhaust.Flue dust is mainly made up of carbon granule.Owing to granule is small, the particulate matter of diesel exhaust very easily sucks, and this causes the healthy danger side of body under higher exposure level.Additionally, SOF contains polycyclic aromatic hydrocarbon, some of them are suspected carcinogens.
Utilize new advanced combustion technology (the such as Diesel engine of homogeneous-charge compression-ignition (HomogeneousChargeCompressionIgnition (HCCI)) by making the temperature of cylinder internal-combustion flame reduce and increase concordance and the degree of mixing of fuel supply before lighting a fire, by can emissions-reducing to the NO outside electromotorxWith particulate matter (PM).Compared with the waste gas of conventional diesel discharge, the waste gas discharged before generally carrying out any process contains the particulate matter and NO that substantially reducex.In some cases, the NO of this advanced burning diesel oil engine emissionxNO than conventional diesel dischargexFew 2 to 3 times.But, combustion process is being changed into relatively low NOxWith in the process of PM discharge, the total amount that CO and hydrocarbon (HC) discharge will increase, and the character of the HC formed will change (being such as likely to produce more methane), and EGT is relatively low.In some cases, CO and the HC discharge capacity of advanced burning diesel oil electromotor than CO and the HC discharge capacity high 50% of conventional diesel to about 100%.Owing to existing Diesel Emissions catalytic article technology is proposed significant challenge by these exhaust gas properties, it is necessary to new catalyst formulation, to meet the rules and regulations of increasingly stringent, for instance Euro6 and USTier2Bin5.
The oxidation catalyst that known utilization comprises the noble metal being applied in advance on refractory metal oxides load is to process the waste gas of Diesel engine, with by hydrocarbon and CO (carbon monoxide converter) gas pollutant oxidation being become carbon dioxide and water and make these pollutant convert.This catalyst is generally contained within and is referred to as diesel oxidation catalyst (DOC) or is more referred to simply as in catalytic conversion agent or catalyst, described catalyst is placed in the exhaust gas flow ducts of diesel powered system, with at waste gas discharged to air before be processed to.Usual diesel oxidation catalyst is formed on the carrier of pottery or metal base (such as such as flow type monolithic carrier described herein below), one or more catalyst wash coat complex of described deposited on supports.Except making gaseous state HC and CO emission and particulate matter (SOF composition) convert, the oxidation catalyst containing platinum group metal (being generally applied on refractory oxide load) promotes that nitric oxide (NO) is oxidized to NO2。
Inefficient for processing the initial cold startup phase that the catalyst of explosive motor waste gas runs at the run duration such as electromotor of relative low temperature, because the temperature of engine exhaust is not high enough to, it is impossible to the conversion of poisonous component in catalytic waste gas effectively.The known oxidation catalyst containing the platinum group metal being applied on refractory oxide load may be used for processing the waste gas of diesel engine emissions.Platinum (Pt) is the effective metal making CO and HC aoxidize after high temperature ageing under lean conditions and under fuel sulfur exists in DOC.On the other hand, for the oxidation of CO and HC, the DOC catalyst rich in Pd generally shows higher ignition temperature, particularly as used for the waste gas (deriving from the fuel of high sulfur content) processed containing high level sulfur or when HC stores and uses together with material." lighting " temperature of specific components is 50% temperature reacted of described component.DOC containing Pd can suppress Pt to make hydrocarbon convert and/or make NOxThe activity of oxidation, and also catalyst can be made sulfur poisoning susceptible more.These characteristics generally prevent the oxidation catalyst rich in Pd in the operating use of lean burn, especially under major part driving conditions, engine temperature is maintained at the light diesel application of less than 250 DEG C.
Although platinum (Pt) for CO and HC have excellent lighting characteristic and thus be for removing the prioritizing selection of noble metal in the catalyst composites of diesel engine exhaust in history, nearest palladium (Pd) causes bigger interest due to its relatively low cost.In some cases, it has proved that palladium be suitable for platinum is simultaneously used in DOC catalyst to reduce the aequum of platinum, although its sulfur is more sensitive and activity slightly weak (based on weight).It is true that the combination of Pt and Pd is more more active than independent Pt.Owing to palladium activity in DOC catalyst is relatively low, it is ensured that it is arranged in DOC catalyst in the way of not suppressing its performance is highly important.
Oxygen storage components (such as cerium) does not generally mix with DOC, because it combines causes that platinum keeps the state of oxidation.Owing to normal Diesel engine runs under lasting lean conditions, platinum has no chance to be reduced into active metallic form.
Along with the rules and regulations increasingly stringent of discharge, exploitation provides the diesel oil oxidation catalysis system of improved performance (such as relatively low ignition temperature) to be persistent goal.Utilizing DOC component (such as palladium) as efficiently as possible is also a target.
Summary of the invention
One aspect of the present invention is for the oxidation catalyst compound for removing engine exhaust emission thing, including the carrier substrate with certain length, arrival end and the port of export, and the diesel oxidation catalyst catalysis material on carrier, including the diesel oxidation catalyst catalysis material in the first washcoat district and the second washcoat district.First washcoat district comprises the first washcoat and the first refractory metal oxides load, and described first washcoat contains one or more in platinum (Pt) and palladium (Pd) component.First washcoat district is adjacent with the arrival end of carrier substrate.Second washcoat district comprises the second washcoat and the second refractory metal oxides load, and described second washcoat contains one or more in platinum and palladium component.Second washcoat district is adjacent with the port of export of carrier substrate.At least the 50% of palladium component total amount is positioned at the first washcoat district, and at least the 50% of platinum component total amount is positioned at the second washcoat district.
In one embodiment, the second washcoat district is substantially free of palladium.In one or more embodiment, the first washcoat district extends to the total length of base material, and the second washcoat district and the first washcoat district is at least some of overlapping.In one or more embodiment, the first washcoat district extends to about the 5% to 95% of length substrate from arrival end, and the second washcoat district extends to about the 5% to 95% of length substrate from the port of export.
In one or more embodiment, the first washcoat district and the second washcoat district are overlapped.Exist from about 1:10 to about 4:1 with the ratio of platinum total amount Yu palladium total amount according to one or more embodiment, platinum and palladium.In one or more embodiment, catalysis material can make HC and CO (the including methane component) oxidation of advanced burning diesel oil engine emission effectively, and the activation of the first washcoat district makes CO and HC aoxidize under the maximum discharge relevant to advanced burning diesel oil electromotor operation and cryogenic conditions.
According to one or more embodiment, one of first refractory metal oxides load and the second refractory metal oxides load or the two comprise aluminium oxide, silicon dioxide, zirconium oxide, titanium dioxide and its combination in one or more, the second refractory oxide load comprise aluminium oxide, silicon dioxide, zirconium oxide, titanium dioxide and its combination in one or more.In one or more embodiment, one of the first washcoat and the second washcoat or the two comprise in zeolite, alkaline-earth oxide, rare earth oxide and base metal oxide further one or more.
In one or more embodiment, complex comprises the priming coat being substantially free of noble's metal component further, and described priming coat is coated on carrier substrate below one of the first washcoat district and the second washcoat district or the two.In one or more embodiment, the first load comprises ceria and the molecular sieve containing zeolite, and described zeolite is selected from beta-zeolite, ZSM-5 or zeolite-Y.According to one or more embodiment, catalyst composites has about 30g/ft3To 350g/ft3The platinum of scope and the total bearing capacity of palladium.
Another aspect of the present invention relates to the method processing conventional diesel waste gas stream or advanced burning diesel oil waste gas stream.One embodiment of method includes making waste gas stream pass through DOC.Waste gas first passes through the first washcoat district comprising the first washcoat and the first refractory metal oxides load, and described first washcoat contains one or more in platinum (Pt) and palladium (Pd) component.Then making the waste gas stream the second washcoat district by comprising the second washcoat and the second refractory metal oxides load, described second washcoat contains one or more in multiple platinum and palladium component.At least the 50% of palladium component total amount is positioned at the first washcoat district, and at least the 50% of platinum component total amount is positioned at the second washcoat district.
In the embodiment of one or more method, the second washcoat is substantially free of palladium.In one or more embodiment of method, it is completely overlapped with the first washcoat district that the first washcoat district extends to the total length of base material and the second washcoat district.Embodiment according to one or more method, the first washcoat district extends to about the 5% to 95% of length substrate from arrival end, and the second washcoat district extends to about the 5% to 95% of length substrate from the port of export.
In the embodiment of one or more method, the first washcoat district and the second washcoat district are overlapped.In the embodiment of one or more method, platinum and palladium are present in whole catalyst composites to about 4:1 from about 1:10 with the ratio of platinum Yu palladium.
Embodiment according to one or more method, one of first refractory metal oxides load and the second refractory metal oxides load or the two comprise aluminium oxide, silicon dioxide, zirconium oxide, titanium dioxide and its combination in one or more, the second refractory oxide load comprise aluminium oxide, silicon dioxide, zirconium oxide, titanium dioxide and its combination in one or more.In the embodiment of one or more method, one of the first washcoat and the second washcoat or the two comprise in zeolite, alkaline-earth oxide, rare earth oxide and base metal oxide further one or more.Embodiment according to one or more method, diesel oxidation catalyst complex comprises the priming coat being substantially free of noble's metal component further, and described priming coat is coated on carrier substrate below one of the first washcoat district and the second washcoat district or the two.
In the embodiment of one or more method, the first load comprises ceria and the molecular sieve containing zeolite, and described zeolite is selected from beta-zeolite, ZSM-5 or zeolite-Y.The embodiment of one or more method can comprise SCR (SCR) catalytic article that diesel exhaust introducing is arranged in catalysis soot filter (CSF) downstream further.The embodiment of one or more method can make CO and HC aoxidize under the maximum discharge relevant to advanced burning diesel oil electromotor operation and cryogenic conditions.
Another aspect of the present invention relates to conventional diesel or advanced burning diesel oil engine exhaust treatment systems.Described system includes being described in catalyst composites type above and soot filter, catalysis soot filter, SCR (SCR) catalytic article and NO according to any of the above embodimentxStore and reduction (NSR) catalytic article in one or more.
Accompanying drawing is sketched
Fig. 1 is the perspective view of honeycomb type refractory support element, and described element comprises diesel oil oxidation catalysis (DOC) the washcoat complex according to the present invention.
Fig. 2 is the partial transectional face view amplifying relative to Fig. 1 and obtaining along the plane parallel with Fig. 1 carrier end face, the zoomed-in view of a gas channel shown in its display Fig. 1.
Fig. 3 A to 3D display cross-sectional view according to the oxidation catalyst compound of the multiple embodiment of the present invention.
Fig. 4 is the diagram that emissions from engines according to an embodiment of the invention processes system.
Fig. 5 is the chart that in the multiple embodiment of the present invention, CO converts.
Fig. 6 is the chart that in the multiple embodiment of the present invention, hydrocarbon converts.
Detailed Description Of The Invention
Before describing several exemplary of the present invention, it will be appreciated that the invention is not restricted to the detailed description of structure or the process steps that middle offer is described below.The present invention can be other embodiments, and can put into practice in many ways or implement.
Embodiment of the present invention relate to the use of catalyst sections scheme, and it can improve Pt/Pd catalyst particularly performance in advanced burn application in diesel engine application.Utilize new advanced combustion technology (the such as Diesel engine of homogeneous-charge compression-ignition (HCCI) by making the temperature of cylinder internal-combustion flame reduce and increase concordance and the degree of mixing of fuel supply before lighting a fire, by can emissions-reducing to the NO outside electromotorxWith particulate matter (PM).But, combustion process is being changed into relatively low NOxWith in the process of PM discharge, the total amount that CO and hydrocarbon (HC) discharge will increase, and the character of the HC formed will change (being such as likely to produce more methane), and EGT is relatively low.Owing to existing Diesel Emissions antigravity system is proposed significant challenge by these exhaust gas properties, it is necessary to new catalyst technology, in order to meet the rules and regulations of increasingly stringent, for instance Euro6 and USTier2Bin5.
Although platinum (Pt) has excellent lighting characteristic for CO and HC and is that nearest palladium causes bigger interest due to its relatively low cost for removing preferred noble metal in the catalyst composites of diesel engine exhaust.For advanced combustion engine, palladium also has advantages over several performance advantages of platinum.Such as, platinum is prone to be suppressed (namely poisoning) by the CO of high concentration, and Pt shows that it is very low as the activity of methane oxidation agent.But, palladium not by CO from suppressing and known it is more more effective to methane oxidation than platinum.Owing to expecting the advanced more CO of burning diesel oil engine emission and methane, Pd is therefore used to have notable benefit.
The zone coated of catalyst wash coat is those skilled in the art to improve catalyst performance under motor instant runs and commonly used technology.This completes usually by by the specific site (or district) that noble metal composite and/or noble metal total amount separate to carrier substrate (such as monolith catalyst honeycomb type carrier).Additionally, zone coated allows to be placed in base metal oxide washcoat material and other washcoat additives the specific site of the noble metal performance that can strengthen institute's load.The noble metal (specifically Pt) of more amount is frequently located in carrier leading portion (import), makes CO and HC aoxidize to reach comparatively fast to light.Palladium is usually located at carrier back segment (outlet) because carrier outlet is normally due to catalyst is lighted thus hotter, and Pd than Pt to thermal sintering more tolerant to.Embodiment of the present invention utilize catalyst sections scheme, by the Pd of high level is placed in carrier front section, the Pt of corresponding high level are placed in carrier back section, increase Pt/Pd preparation performance in diesel fuel applications.This partition scheme is used in particular for eliminating the high levels of CO relevant to advanced burning diesel oil electromotor and HC (particularly methane).High levels of CO and HC owing to deriving from electromotor are reacting through the Pd inlet region strengthened, and corresponding higher local temperature desired on this position metallic site will increase the oxidation of methane, even at waste gas bulk temperature relatively low time.Additionally, when CO and HC is dense, at low exhaust-gas temperatures that CO is poisoning less sensitive through the import of high level Pd strengthening.
The partition scheme of the present invention is contrary with tradition instruction, and major part platinum is placed in the hottest part of carrier that sintering more likely occurs by it.The subregion of palladium and platinum is placed and is made catalytic component produce CO and HC conversion ratio high unexpectedly, even after aging.
The scope of the multiple embodiment of the present invention includes all of catalyst washcoat layer formula and complex, wherein front portion (import) section being positioned at carrier substrate more than about 50% of palladium total amount, platinum total amount be positioned at rear portion (outlet) section more than about 50%.Unexpectedly, the exit zone without palladium demonstrates the highest CO and HC conversion ratio.More unexpectedly, embodiment of the present invention show outstanding CO and HC conversion ratio in standard diesel engine.
In one or more embodiment, the secondth district is substantially free of oxygen storage components.In one or more embodiment, the secondth district is substantially free of palladium.In one or more embodiment, the firstth district is substantially free of molecular sieve or zeolite.In one or more embodiment, the secondth district is substantially free of the component of the carried noble metal of nonzeolite.In one or more embodiment, one of the firstth district and the secondth district or the two be substantially free of non-noble metal components.In one or more embodiment, diesel oxidation catalyst material is substantially free of NOx(nitrogen oxides) stores the base metal of Sq, and described base metal includes but not limited to Ba, Mg, K and La etc..In other embodiments, catalysis material not rhodium-containing.In one or more embodiment, zeolite includes beta-zeolite, ZSM-5 or zeolite-Y.
In the particular of the present invention, catalyst composites, antigravity system and method are particularly well-suited to process advanced burning diesel oil engine exhaust emission thing, its feature and be different from conventional diesel waste gas be its HC and CO discharge capacity higher (in some cases high 50% to 100%) and NOxDischarge capacity relatively low (low 2 to 3 times in some cases).Similarly, one embodiment of the invention relates to process the oxidation catalyst compound of advanced burning diesel oil engine exhaust emission thing, it carrier substrate including there is certain length, arrival end and the port of export, and the diesel oxidation catalyst catalysis material on carrier, described diesel oxidation catalyst catalysis material includes the first washcoat district and the second washcoat district.First washcoat district comprises the first washcoat and the first refractory metal oxides load, described first washcoat contains one or more in platinum (Pt) and palladium (Pd) component, and the first washcoat district is adjacent with the arrival end of carrier substrate.Second washcoat district comprises the second washcoat and the second refractory metal oxides load, and described second washcoat contains one or more in platinum and palladium component, and the second washcoat district is adjacent with the port of export of carrier substrate.Wherein at least the 50% of palladium component total amount is positioned at the first washcoat district, and at least the 50% of platinum component total amount is positioned at the second washcoat district.
In a more particular embodiment, the second washcoat district is substantially free of palladium.In a more particular embodiment, the first washcoat contains the mixture of Pt and Pd, and has the activity making CO and HC aoxidize under the maximum discharge relevant to advanced combustion engine operation and cryogenic conditions.The heat of the first washcoat release can help the methane component in diesel exhaust to aoxidize.According to an embodiment, in waste gas, the burning of waste gas component is enough to the localized heat release producing to be enough to make methane component aoxidize.In particular embodiments, the first washcoat extends from arrival end along base material upstream portion, and the second washcoat district extends from the port of export along base material downstream part.
Involved catalyst composites or catalytic article refer to the catalytic article of carrier substrate (such as honeycomb type base material), it has one or more washcoat containing catalyst component, described catalyst component such as can effectively catalysis HC and CO oxidation noble metal component.
Involved " substantially without ", " being substantially free of " refer to that described material is not intended that and are provided in described layer.It will be appreciated that be, it is believed that be trace (namely < the 10% of material, 9%, 8%, 7%, %, 5%, 4%, 3%, 2% or even 1%) described material can shift or diffuse to described layer.
Refractory metal oxides load refer to aperture more thanAnd the load granule that pore-size distribution is wider.As defined herein, this metal oxide supported body does not include molecular sieve, particularly zeolite.In certain embodiments, high-specific surface area refractory metal oxides load can be used, such as alumina support materials, is also referred to as " gama-alumina " or " aluminium oxide of activation ", and it generally shows the BET surface area (" m with 60 square metres more than every gram2/ g "), generally to about 200m2/ g or higher.The aluminium oxide of this activation is usually γ phase and the mixture of δ phase alumina, it is also possible to containing substantial amounts of η phase, κ phase and θ phase alumina.Refractory metal oxides except the aluminium oxide of activation can serve as the load of at least some of catalyst component in special catalyst.For example, as it is known that substantial amounts of ceria, zirconium oxide, Alpha-alumina and other materials can so use.Although much all having the shortcoming that BET surface area is substantially less than the aluminium oxide of activation in these materials, but this shortcoming is tended to or performance higher by obtained catalyst durability and is increased and offset." BET surface area " has and passes through N2The general sense of indication in Brunauer, Emmett, Teller method of determining adsorption surface area.BET type N can also be utilized2Absorption or desorption experiment measure bore dia and pore volume.
As used herein, molecular sieve (such as zeolite) refers to the material of carried catalytic noble metal in particulate form, and this material has substantially uniform pore-size distribution, and its mean pore size is no more thanIn involved catalyst layer, " nonzeolite load " refers to the material of non-molecular sieve or nonzeolite, and this material is by combining, disperse, impregnating or other proper method carried noble metal, stabilizer, accelerator, binding agents etc..The example of this load includes but not limited to high-specific surface area refractory metal oxides.One or more embodiment of the present invention includes the high-specific surface area refractory metal oxides load comprising activating compounds, and described compound is selected from following group: aluminium oxide, zirconium oxide, silicon dioxide, titanium dioxide, silica-alumina, Zirconia-alumina, titania-alumina, lanthana-alui, lanthana-zirconia-aluminium oxide, baria-alumina, baria lanthana-alumina, baria lanthana-Dineodymium trioxide-aluminium oxide, zirconia-coated silica, titania-silica or zirconia-titania.
Involved " dipping " refers in the hole that the solution containing noble metal is placed in material (such as zeolite or nonzeolite load).In the embodiment described in detail, by the just wet dipping being impregnated with noble metal, wherein contain the volume after the solution dilution of noble metal roughly equal with the pore volume of load.Just wet impregnation generally makes precursor solution be distributed in the hole system of material substantially uniformly.The additive method adding noble metal is also known in the art and can use.
Involved OSC (oxygen storage components) refers to have multivalent state and active with oxidant (such as oxygen or nitrous oxide) under oxidative conditions can react or can enliven the material of reaction with reducing agent (such as carbon monoxide (CO) or hydrogen) under the reducing conditions.Usual oxygen storage components comprises one or more oxides of one or more rare earth metals.The example of suitable oxygen storage components includes ceria, zirconium oxide and its combination.Praseodymium oxide is also used as OSC or accelerator.OSC can comprise one or more accelerator or improve agent, for instance Y, La, Nd, Sm, Pr and its combination.OSC can be contained in any layer, particularly when the activating agent of Pd contained during it is as those layers.
Involved " advanced burning diesel oil electromotor " is different from conventional diesel, including homogeneous-charge compression-ignition (HCCI), premixed charge compression ignition (PCCI) and low-temperature burning (LTC) electromotor, concordance and the degree of mixing of its temperature reduction and increase fuel supply by making cylinder internal-combustion flame before lighting a fire run.The multiple variant of advanced combustion technology is to it known in the art, listed above being not meant to include all variants.The feature of advanced burning diesel oil engine exhaust be different from conventional diesel waste gas be its HC and CO discharge capacity compared with conventional diesel higher (in some cases high 50% to 100%) and NOxDischarge capacity relatively low (low 2 to 3 times in some cases).More specifically, in newly discharging driving cycle (NEDC), the emission of generally advanced burning vehicle is characterized by containing < the NO of 0.18g/kmx, > CO of 2.5g/km and > HC of 0.5g/km.In advanced combustion engine, particulate matter also substantially reduces.Although the emission of lean burn advanced person's burning diesel oil electromotor is more like with the emission of spark ignition stoichiometric gasoline electromotor, but engine operation mode is diverse, thus exhaust-gas treatment scheme is also diverse.What skilled artisans will appreciate that is, advanced burning diesel oil electromotor is different from conventional diesel and gasoline fire spark ignition engine, its exhaust gas properties and engine operation mode are by needing and processing schemes used different in former diesel oil and spark ignition engine and/or catalyst composites, effectively to process HC, CO and NOx。
The component of exhaust-gas treatment thing and system is described in detail below according to embodiment of the present invention.
Carrier
According to one or more embodiment, carrier can be typically used for preparing any material of DOC catalyst, it is preferable that comprises metal or ceramic honeycomb type structure.Can using any suitable carrier, for instance have the monolithic carrier of gas channel tiny and parallel in a large number, described passage extends through from carrier inlets or outlets face, so that passage is open, it is possible to make fluid flow wherein.Passage is substantially straight path from its fluid inlet to its fluid issuing, and it is defined as catalysis material and is coated on above in " washcoat " mode so that the wall that contacts with catalysis material of the gas that flows through passage.The flow channel of monolithic carrier is thin-walled channels, and it can be any suitable transverse cross-sectional shape and size, for instance trapezoidal, rectangle, square, sinusoidal, hexagon, ellipse, annular etc..This structure can contain about 60 to about 600 or more gas access end (i.e. " hole ") in cross section per square inch.
Ceramic monolith can be prepared by any suitable refractory material, for instance cordierite, cordierite-Alpha-alumina, silicon nitride, corundum, zirconium mullite, spodumene, magnesia-alumina-silica, silicic acid zircon, sillimanite, magnesium silicate, zircon, petalite, Alpha-alumina, aluminium silicate etc..
Metalline is can also is that, it is possible to nonmetal comprise one or more metals or metal alloy for the carrier of layered catalyst complex in the present invention.The metallic carrier of various shape can be used, for instance corrugated lamella or monolithic form.Suitable metal load body includes heating resisting metal and metal alloy, for instance titanium and rustless steel and containing a large amount of ferrum or using ferrum as other alloys of key component.This alloy can contain one or more in nickel, chromium and/or aluminum, and the total amount of these metals advantageously comprises the alloy of at least 15 weight %, for instance the nickel of the chromium of 10-25 weight %, the aluminum of 3-8 weight % and at most 20 weight %.Alloy can contain one or more other metals a small amount of or trace, for instance manganese, copper, vanadium, titanium etc..Surface or metallic carrier can in high temperature (such as 1000 DEG C or higher) oxidation, to put forward heavy alloyed corrosion resistance by forming oxide skin(coating) at carrier surface.The oxidation of this high temperature induction can strengthen refractory metal oxides load and promote the metal component of catalysis and the bonding of carrier.
The preparation of catalyst composites
The catalyst composites that can make the present invention forms monolayer or multilamellar.In some cases, it is suitable for preparing the slurry of catalysis material, and utilizes this slurry to form multilamellar on carrier.The process that can pass through to know easily prepares complex.Illustrated below is a kind of exemplary process.Term used herein " washcoat " has the general sense of this area, refer to the thin attachment washcoat of the catalysis material being coated on substrate carrier material or other materials, described substrate carrier material such as honeycomb type carrier element, its sufficiently porous is to allow pending air-flow traverse passage.
Catalyst composites layer can be easily prepared on monolithic carrier.For the ground floor of specific washcoat, in suitable medium (such as water), the granule that grinds of high-specific surface area refractory metal oxides (such as gama-alumina) is made slurry.Then make carrier dip one or many in this slurry or be coated on carrier by slurry, so that the desired amount of metal-oxide is deposited on carrier, for instance about to dip about 0.5 to about 2.5g/in every time3.In order to make component (such as noble metal (such as palladium, rhodium, platinum and/or its combination) and stabilizer and/or accelerator) merge, it is possible to before being coated on carrier, these components are blended in slurry with the form of mixtures of water solublity or dispersible compounds or complex.Thereafter by heating, the carrier through coating is calcined, for instance carry out about 10 minutes to about 3 hours in 400-600 DEG C.Generally when needs use palladium, use the palladium component of compound or composite form, so that component is scattered on refractory metal oxides load (aluminium oxide such as activated).For the purposes of the present invention, term " palladium component " decomposes or changes into any compound of catalysis activity form, complex or similar when referring to after calcining or use, be usually metal or metal-oxide.The water soluble compound of metal component or dispersible compounds or complex can be used, if volatilization or decompose other components removed from metal component reversible reaction will not occur after impregnating or make liquid medium that metal component is deposited on refractory metal oxides load granule and metal or its compound or its complex or being present in catalyst composites and can pass through to heat and/or in vacuum is applied.In some cases, until catalyst comes into operation and is in operation just can complete the removal of liquid when running into high temperature.Usually, from the angle of economics and environment aspect, it is possible to use the aqueous solution of precious metal soluble compound or complex.The indefiniteness example of suitable compound includes Palladous nitrate., four ammino Palladous nitrate .s, platinum chloride and platinum nitrate.In calcining step or at least at the initial stage using complex, this converting compounds becomes the catalysis activity form of metal or its compound.
In the preparation present invention, a kind of proper method of layered catalyst complex any layer is to prepare the mixed solution of required precious metal chemical complex (such as palladium compound) and at least one load, high-specific surface area refractory metal oxides load (such as gama-alumina) that described load such as grinds, its sufficiently dry, can absorbing essentially all of solution to form moistening solid, described moistening solid mixes with water subsequently so that formed can the slurry of washcoat.In one or more embodiment, slurry is acid, has such as about 2 to the pH value less than about 7.Can by the mineral acid of q.s or organic acid addition slurry making the pH value of slurry reduce.When considering the compatibility of acid and raw material, it is possible to use combination.Mineral acid includes but not limited to nitric acid.Organic acid includes but not limited to acetic acid, propanoic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, tartaric acid, citric acid etc..Afterwards if it is required, water solublity or dispersible compounds and/or stabilizer (such as Barium acetate) and accelerator (such as Lanthanum (III) nitrate) are added in slurry.
In one embodiment, afterwards slurry is ground, so that essentially all solid has the average diameter granular size less than about 20 microns, namely between about 0.1-15 micron.Can be ground in ball mill or other similar equipment, and the solids content of slurry can be such as about 20-60 weight %, more specifically about 30-40 weight %.
Can utilize and prepare on the first layer and deposition of additional layer with the same procedure at deposited on supports ground floor described above, be i.e. the second layer and third layer.
After washcoat, it is possible to use methods known in the art prepare subregion catalyst substrate, for instance as described in the 7th, 189, No. 376 United States Patent (USP), it is as entirely through being incorporated herein by reference.
As noted above, nearest palladium (Pd) starts to cause bigger interest due to its relatively low cost.But, when cost is not design vehicle catalyst composites, need the single factor considered.No matter cost size, if specific catalyst material is prone to poisoning or degraded in specific engine exhaust environment, then if catalyst composites over time will poisoning or degraded; catalyst composites will not use this certain material.In the embodiment relevant to advanced burning diesel oil electromotor, Pd has advantages over several performance advantages of platinum.Such as, platinum is prone to be suppressed (namely poisoning) by the CO of high concentration, and Pt makes the ability of methane oxidation very low.On the other hand, Pd not by CO from suppressing and known it is more more effective to methane oxidation than platinum.Owing to expecting the advanced more CO of burning diesel oil engine emission and methane, Pd is therefore used to have notable benefit.
Owing to combustion characteristics in cold start conditions is unstable, advanced combustion engine is likely to start in normal mode, and this produces less CO and HC emission.Electromotor enters " advanced combustion mode " as early as possible (after such as 1-2 minute), with the NO outside emissions-reducing to electromotorxAnd PM.Catalyst must keep activity under two kinds of operational modes, and is thus able to process CO and HC emission to greatest extent.Although the conventional catalyst based on Pt or Pt/Pd demonstrates the premium properties processing CO and HC under common diesel service condition, its ignition temperature significantly improves when CO and the HC level being discharged into outside electromotor is higher.Additionally, once catalyst is activated and function in " advanced combustion mode ", one can make these components aoxidize surely effectively, and the bulk temperature outside even along with electromotor declines.
The catalyst composites of one or more embodiment according to the present invention it is easier to understand with reference to Fig. 1 and Fig. 2.Fig. 1 and 2 shows refractory support element 2 according to one embodiment of the invention.With reference to Fig. 1, refractory support element 2 is cylindrical, and it has cylindrical outer surface 4, upstream face 6 and the downstream end face 8 identical with end face 6.Carrier element 2 has gas channel 10 tiny and parallel in a large number formed therein.As seen in Figure 2, gas channel 10 is formed by wall 12, and extends to downstream end face 8 carrier 2 from upstream face 6, and passage 10 is unimpeded, to allow fluid (such as air-flow) longitudinally to flow through carrier 2 by gas channel 10.It is more easy in Fig. 2 and sees, the size of wall 12 and setting make gas channel 10 have the polygonal shape of fundamental rule, are substantially foursquare in the embodiment described, but according to J.C.Dettling equal to the authorize June 15 nineteen eighty-two the 4th, 335, No. 023 United States Patent (USP)s have fillet.The first washcoat 14 being referred to as " washcoat " under this area and following certain situation is attached to the wall 12 of carrier element or is coated onto.As shown in Figure 2, the second washcoat 16 is coated on the first washcoat 14 as described above.In one embodiment, it is possible to priming coat (not shown) is applied to below base material the first washcoat 16.
As shown in Figure 2, carrier element includes the void space that gas channel 10 is formed, and the thickness of the wall 12 of the region, cross section of these passages 10 and restriction passage is different in a kind of carrier element type and in another kind.Similar, on carrier, the weight of the washcoat of coating changes in varied situations.Therefore, in describing washcoat or catalytic metal component or complex during the amount of other components, using the composition weight unit in the catalyst carrier of per unit volume is easily.Therefore, every cubic inch of (" g/in of unit of gram used herein3") and gram every cubic feet of (" g/ft3") refer to the composition weight of every volume of vehicle element (including the volume in carrier element void space).
In another embodiment, the washcoat of the present invention can zone coated, wherein the first washcoat is at the upstream extremity of carrier substrate, and the second washcoat is in the downstream of carrier substrate.Such as, upstream washcoat can cover base material upstream zone, and downstream washcoat can cover base material downstream section.In such an implementation, second washcoat of the present invention or downstream washcoat can cover the first washcoat or upstream washcoat at least in part.
Can be more easily understood comprising the catalyst composites embodiment of upstream and catchment with reference to Fig. 3 A to 3D.Fig. 3 A shows an embodiment of the zoned oxidation catalyst complex 20 for removing engine exhaust emission thing.Carrier substrate 22 comprises the washcoat of two zone coated separated, described carrier substrate such as honeycomb type monolithic, and it has arrival end or upstream extremity 25, the port of export or downstream 27 and the axial length extended between arrival end 25 and the port of export.First washcoat 24 and the second washcoat 26 are coated on base material 22.First washcoat 24 extends from arrival end or upstream extremity 25, wherein contains the first refractory metal oxides load, and described load comprises one or more in platinum (Pt) component and palladium (Pd) component.Second washcoat 26 extends from the port of export or downstream 27, wherein contains the second refractory metal oxides load, and described load comprises one or more in platinum (Pt) component and palladium (Pd) component.In the embodiment shown by Fig. 3 A, the second washcoat district 26 is overlapping with the first washcoat district 24 at least in part.Catalyst composites containing at least about the 50% of whole palladium components, contains at least about the 50% of platinum component in the first washcoat district 24 in the second washcoat district 26.In an embodiment described in detail, the second washcoat is substantially free of palladium.
In some specific embodiments, the first washcoat district 24 covers the total length of base material 22, and the second washcoat district 26 covers the partial-length of base material 22.In other specific embodiments, the first washcoat district 24 covers the partial-length of base material 22, and the second washcoat district 26 covers the total length of base material 22.First first washcoat district 24 or the second washcoat district 26 all can be coated on base material 22, and another washcoat overlaps or contacts.
The length in washcoat district, upstream 24 can also describe to the percentage ratio of downstream edge length with catalysis element upstream.Washcoat district, usual upstream 24 includes about the 5% to about 95% of substrate loading 22 total length.Further illustrate washcoat district, upstream 24 and reach about 20%, about 40% and about the 60% of base material 22 length.Washcoat district, downstream 26 covers base material 22 and remains downstream part.Therefore, downstream washcoat district 26 can include the 95% to about 5% of base material 22 axial length.
According to other embodiments, as shown in Fig. 3 B, priming coat 28 can be coated on base material prior to the first washcoat district 24 or the second washcoat district 26, no matter is first coated with which washcoat district.In a specific embodiment, priming coat is without the noble metal component being deliberately added in priming coat complex.Such as, priming coat can comprise refractory metal oxides load.By spreading or migrating, base coat layer 28 can exist some palladiums in the first washcoat or platinum.The combination in the first washcoat district 24 and the second washcoat district 26 can as above described by Fig. 3 A.
With reference to Fig. 3 C, it is shown that an optional washcoat scheme.In this embodiment, the first washcoat district 24 extends from arrival end to the port of export.Second washcoat district 26 is adjacent with the first washcoat district and downstream.First washcoat district 24 can at least in part with the second washcoat area overlapping.In one embodiment, the first washcoat district 24 comprises the first refractory metal oxides load, and described load comprises at least one in platinum and palladium component.Second washcoat district 26 comprises at least one in the second refractory oxide load and platinum and palladium component.In an embodiment described in detail, the ratio of platinum total amount and palladium total amount is between about 10:1 to about 1:4,4:1 to about 1:10 or 1:4 to about 4:1.This ratio can also in the scope of about 3:1 to about 1:3, about 2:1 to about 1:2 and about 1:1.First washcoat district can extend to about the 5% to about 95% of base material 22 axial length from arrival end 25.Second washcoat district 26 extends from the port of export 27, and the second washcoat district 26 can extend from about the 5% of base material 22 axial length to about 95%.
Fig. 3 D shows an embodiment of the first washcoat district 24 and the second washcoat district 26 length along carrier substrate 22 registration.First washcoat district 24 of particular extends to about the 5% to about 95% of base material 22 length from the arrival end 25 of base material 22.Second washcoat district 26 extends about the 5% to about 95% of base material axial length from the port of export 27 of base material 22.The combination of the first washcoat and the second washcoat can as above described by Fig. 3 A to 3C.
In first washcoat and the second washcoat, the bearing capacity of component is as follows.
In first washcoat, Pd component can with about 10g/ft3To 200g/ft3The amount existence of scope (includes 20,30,40,50,60,70,80,90,100,110,120,130,140,150,160,170,180 and 190g/ft3).Pt component can with about 10g/ft3To 140g/ft3The amount of scope exist (include 20,30,40,50,60,70,80,90,100,110,120,130g/ft3).Total bearing capacity of palladium and platinum is about 20g/ft in certain aspects3To 400g/ft3Scope (include 30,40,50,60,70,80,90,100,110,120,130,140,150,160,170,180,190,200,210,220,230,240,250,260,270,280,290,300,310,320,330,340,350,360,370,380 and 390g/ft3)。
Refractory oxide load (such as aluminium oxide) can with about 0.1 to about 3g/in3Scope exist, scope is about 0.5 to about 2g/in more specifically3.Molecular sieve (such as H-beta-zeolite) can with about 0.1 to about 1g/in3Scope exist, scope is about 0.2 to about 0.5g/in more specifically3.In multiple embodiments, the load of the first washcoat and/or the second washcoat comprises one or more in zeolite, alkaline-earth oxide, rare earth oxide and base metal oxide further.In the embodiment of other detailed descriptions, described load comprises ceria and molecular sieve further, and described molecular sieve comprises the zeolite selected from beta-zeolite, ZSM-5 or zeolite-Y.
Diesel oxidation catalyst (DOC) complex of the present invention may be used in the integrated emission treatment systems comprising one or more supplementary elements, to process diesel exhaust emission.Such as, emission treatment systems can comprise soot filter component and/or SCR (SCR) catalytic article further.Diesel oxidation catalyst may be located at upstream or the downstream of soot filter and/or SCR component.
Outside processing exhaust emissions other than with oxidation catalyst, the present invention also utilizes soot filter to remove particulate matter.Soot filter may be located at DOC upstream or downstream, but soot filter is usually located at diesel oxidation catalyst downstream.In one embodiment, soot filter is catalysis soot filter (CSF).CSF can comprise the base material scribbling washcoat, and described washcoat contains for burning the flue dust caught and/or one or more catalyst making exhaust flow thing aoxidize.Usually, soot combustion catalyst agent could be for any of catalyst of burning soot.Such as, CSF can scribble for making unburned hydrocarbon and making one or more high-specific surface area refractory oxides (such as aluminium oxide or ceria-zirconia) of PM combustion to a certain extent.Soot combustion catalyst agent can be the oxidation catalyst comprising one or more noble metals (PM) catalyst (platinum, palladium and/or rhodium).
Usually, it is possible to use any of filter base material in this area, including such as honeycomb type wall-flow filter, wire wound or filled type fabric filter, open celled foam, sintered metal filter etc., it is preferred to use wall-flow filter.Wall flow substrate for load C SF complex has the tiny and substantially parallel gas channel extended along the base material longitudinal axis.Usual each passage is closed in one end of substrate body, closes at opposite end face with its staggered passage.This monolithic carrier can contain cross section per square inch about 700 or more gas channel (or " hole "), although the quantity of much less can be used.Such as, carrier can have about 7 to 600, more generally about 100 to 400 holes (" cpsi ") per square inch.The cross section in hole can be rectangle, square, annular, ellipse, triangle, hexagon or other polygons.Wall flow substrate is generally of the thickness between 0.002 and 0.1 inch.Preferred wall flow substrate has the thickness between 0.002 and 0.015 inch.
Usual wall-flow filter base material is made up of Ceramic Like material, for instance cordierite, Alpha-alumina, corundum, silicon nitride, zirconium oxide, mullite, spodumene, magnesia-alumina-silica or silicic acid zircon, or the refractory metal of porous.Wall flow substrate can also be formed by ceramic fibre composite materials.Preferred wall flow substrate is formed by cordierite and corundum.This material can have tenable environment, the high temperature run into when particularly processing waste gas stream.
The exhaust treatment system of the present invention can comprise SCR (SCR) component further.SCR component may be located at upstream or the downstream of DOC and/or soot filter.Preferred SCR component is positioned at the downstream of soot filter component.For the suitable SCR catalyst component in emission treatment systems can under 600 DEG C of temperature below catalysis NO effectivelyxThe reduction reaction of component so that even under the relevant low load condition of usual and relatively low EGT to high-caliber NOxProcess.The preferably amount according to the reducing agent in addition system, catalytic article can by the NO of at least 50%xComponent is converted into N2.Another desirable attributes of this complex is that it has catalysis O2With arbitrarily excessive NH3It is reacted to N2And H2The ability of O, so that NH3Will not be discharged in air.May be used for the SCR catalyst complex of emission treatment systems and also should have the thermostability to 650 DEG C of temperatures above.This high temperature is likely encountered in upstream catalyst soot filter regenerative process.
Suitable SCR catalyst complex is described in such as the 4th, 961, No. 917 United States Patent (USP) (' 917 patent) and the 5th, 516, No. 497 United States Patent (USP) in, both as entirely through being incorporated herein by reference.Complex disclosed in the patent of ' 917 comprises the one in ferrum and copper accelerator or two kinds, and its amount being present in zeolite is about 0.1 to 30 percentage by weight that accelerator adds zeolite gross weight, it is preferable that about 1 to 5 percentage by weight.Except catalysis NOxAnd NH3Reduction becomes N2Outside, disclosed complex can also promote excessive NH3With O2There is oxidation reaction, especially for those complex that promoter concentration is higher.This system comprises NO furtherxStore and release (NSR) catalytic article.In certain embodiments, system comprises the one in SCR or NSR catalytic article or another kind.
In one embodiment, the present invention relates to the emission treatment systems comprising one or more supplementary elements, to process diesel exhaust emission.Fig. 4 can more easily understand a kind of exemplary emission treatment systems by reference, and described Fig. 4 describes the diagram of emission treatment systems 32 according to this embodiment of the present invention.With reference to Fig. 4, containing gas pollutant (such as unburned hydrocarbon, carbon monoxide and NOx) and the waste gas stream of particulate matter be sent to the diesel oxidation catalyst (DOC) 38 of the Novel washing coating composite scribbling the present invention from electromotor 34 by line 36.In DOC38, unburned gaseous state and fixed hydrocarbon (i.e. SOF) and the burning of carbon monoxide major part form carbon dioxide and water.Additionally, NOxA part of NO of component can be oxidized into NO in DOC2.Then waste gas stream is sent to the catalysis soot filter (CSF) 42 catching the internal particulate matter existed of waste gas stream by line 40.Optionally, CSF42 is carried out catalysis, so that its passive regeneration.After removing particulate matter by CSF42, waste gas stream is sent to downstream SCR (SCR) element 16 by line 44, with to NOxCarry out processing and/or converting.DOC38 may be at close-coupled position.
One or more embodiment of the present invention relates to process and comprises CO, HC and NOxThe method of diesel exhaust stream.First waste gas stream DOC the first washcoat district by comprising a washcoat (containing one or more in platinum and palladium component) and a kind of refractory metal oxides load is made.Then waste gas is made to pass through to comprise the second washcoat district of the second washcoat (containing one or more in platinum and palladium component) and the second refractory metal oxides load.The distribution of metal make in the first washcoat containing at least about the 50% of palladium total amount and second in washcoat containing at least about the 50% of platinum total amount.
In other embodiments, the diesel exhaust stream after contacting with the second washcoat is introduced the catalysis soot filter (CSF) being positioned at diesel oxidation catalyst downstream.In further embodiment, the diesel exhaust stream after contacting with catalysis soot filter (CSF) is introduced SCR (SCR) component being positioned at catalysis soot filter (CSF) downstream.
DOC catalyst composites disclosed herein can serve as stable Close-coupled catalyst.Close-coupled catalyst and electromotor are closely placed, and allow it to reach as early as possible reaction temperature.In certain embodiments, within Close-coupled catalyst is positioned over 3 feet of electromotor, more specifically within 1 foot, and more specifically distance electromotor less than 6 inches.Close-coupled catalyst is typically directly attached in exhaust manifold.Due to it with electromotor closely, it is preferable that Close-coupled catalyst is at high temperature stable.
Described in particular general's embodiment below according to the present invention.Embodiment is merely illustrative, and is not meant to limit remainder disclosed herein by any way.Although this specification emphasizes to make the pollutant oxidation of Diesel engine, oxidation catalyst described herein may be used for other catalytic reactions, for instance the oxidation of CO and hydrocarbon in petrol engine.
Before describing several exemplary of the present invention, it should be appreciated that the details of the structure of middle elaboration or process steps is described below and is not limiting as the present invention.The present invention can be other embodiments and can implement in many ways.Provided below is the decision design of layered catalyst, including the such as cited complex being used alone or unrestrictedly combine use, its purposes includes the otherwise system and method for the present invention.
Embodiment
Reference sample A
Be multiplied by length 6 by the water paste containing Pt and Pd being applied to " diameter 4.66 " " " cordierite honeycomb type single substrate (400cpsi, wall thickness 4mil) on, utilize the homogeneous mixture of the Pd on OSC and the Pt on aluminium oxide to prepare the Pt/Pd catalyst composites of washcoat.Total bearing capacity of noble metal is 110g/ft3, Pt/Pd ratio is 1:2.Water paste preparation containing Pt and Pd is as follows:
The first wet impregnation technology water solublity Pd salt dipping utilizing standard containing 20% ceria, 6% Dineodymium trioxide, 6% lanthana and 68% zirconium oxide and has about 90m2The OSC material of the BET surface area of/g.Respectively, the first wet impregnation technology water solublity Pd salt dipping utilizing standard has about 150m2The BET surface area of/g, about 0.4cc/g pore volume and aboutThe high-specific surface area gama-alumina of average pore size.This powder is impregnated further with mineral acid.Pd/OSC and the Pt/ aluminium oxide obtained is impregnated powder be placed in the DI water containing zirconium acetate (with ZrO2Total slurry solids that weight calculates is 5%), and make the pH value of the water paste obtained be down to 3.7 by adding organic acid.Utilize methods known in the art by grind by 90% granular size be reduced to less than 10um after, utilize also be that slurry is applied in cordierite substrates by deposition process known in the art.Make the monolithic through coating dry, and then calcine 1h in 550 DEG C.After calcining, total bearing capacity of washcoat is about 1.6g/in3, wherein OSC material contains about 1.0g/in3, aluminium oxide contains 0.5g/in3.By similar approach, the second layer is applied on ground floor, and makes the monolithic of twice coating dry, again calcine 1h in 550 DEG C.After calcining, total bearing capacity of second layer washcoat is about 1.6g/in3, wherein OSC material contains about 1.0g/in3, aluminium oxide contains 0.5g/in3。
Reference sample B
Be multiplied by length 6 by the water paste containing Pt and Pd being applied to " diameter 4.66 " " " cordierite honeycomb type single substrate (400cpsi, wall thickness 4mil) on, utilize the homogeneous mixture of the Pd on OSC, the Pt on aluminium oxide and beta-zeolite to prepare the Pt/Pd catalyst composites of washcoat.Total bearing capacity of noble metal is 150g/ft3, Pt/Pd ratio is 1:2.Water paste preparation containing Pt and Pd is as follows:
The first wet impregnation technology water solublity Pd salt dipping utilizing standard containing 20% ceria, 6% Dineodymium trioxide, 6% lanthana and 68% zirconium oxide and has about 90m2The OSC material of the BET surface area of/g.Respectively, the first wet impregnation technology water solublity Pd salt dipping utilizing standard has about 150m2The BET surface area of/g, about 0.4cc/g pore volume and aboutThe high-specific surface area gama-alumina of average pore size.This powder is impregnated further with mineral acid.Pd/OSC and the Pt/ aluminium oxide obtained is impregnated powder be placed in the DI water containing zirconium acetate (with ZrO2Total slurry solids that weight calculates is 5%), and make the pH value of the water paste obtained be down to 3.7 by adding organic acid.Utilize methods known in the art by grind by 90% granular size be reduced to less than 10um after, add dry H-β zeolite.Further by grind by 90% granular size be reduced to less than 9um after, utilize also be that slurry is applied in cordierite substrates by deposition process known in the art.Make the monolithic through coating dry, and then calcine 1h in 550 DEG C.After calcining, total bearing capacity of washcoat is about 1.6g/in3, wherein OSC material contains about 0.75g/in3, aluminium oxide contains 0.5g/in3, H-beta-zeolite contains 0.25g/in3.By similar approach, the second layer is applied on ground floor, and makes the monolithic of twice coating dry, again calcine 1h in 550 DEG C.After calcining, total bearing capacity of second layer washcoat is about 1.6g/in3, wherein OSC material contains about 0.75g/in3, aluminium oxide contains 0.5g/in3, H-beta-zeolite contains 0.25g/in3。
Reference sample C
Be multiplied by length 6 by the water paste containing Pt being applied to " diameter 4.66 " " " cordierite honeycomb type single substrate (400cpsi, wall thickness 4mil) on, utilize the homogeneous mixture preparation only washcoat catalyst composites containing Pt of the Pt on silica-alumina and beta-zeolite.Total bearing capacity of noble metal is 110g/ft3.Water paste preparation containing Pt is as follows:
The first wet impregnation technology water solublity Pt salt dipping utilizing standard has about 120m2The BET surface area of/g, about 0.7cc/g pore volume and more thanAverage pore size high surface area silica-aluminium oxide (silicon dioxide of 5%).This powder is impregnated further with mineral acid.The Pt/ silica-alumina obtained is impregnated powder be placed in the DI water containing H-beta-zeolite, and make the pH value of the water paste obtained be down to 4 by adding organic acid.Utilize methods known in the art by grind by 90% granular size be reduced to less than 12um after, utilize also be that slurry is applied in cordierite substrates by deposition process known in the art.Make the monolithic through coating dry, and then calcine 1h in 500 DEG C.After calcining, total bearing capacity of washcoat is about 1g/in3, wherein silica-alumina contains about 0.75g/in3, H-beta-zeolite contains 0.25g/in3.By similar approach, the second layer is applied on ground floor, and makes the monolithic of two washcoat dry, again calcine 1h in 500 DEG C.After calcining, total bearing capacity of second layer washcoat is about 1g/in3, wherein silica-alumina contains about 0.75g/in3, H-beta-zeolite contains 0.25g/in3。
Subregion sample D-G
After CO and HCNEDC performance is measured, each sample in reference sample A, B and C is cut in half along length (i.e. the point of mid-length), is multiplied by length 3.0 producing " width 4.66 " corresponding with reference sample A-C first half section and second half section " " coated monolithic.Then these are back-to-back combined into specific combination, produce comparative example D, E, F and G, to simulate different section configurations.Comparative example D includes the first half section (only containing Pt) of reference sample C and the second half section of reference sample A.On the contrary, comparative example E includes the first half section of reference sample A and the second half section (only containing Pt) of reference sample C.Comparative example F includes the first half section (only containing Pt) of reference sample C and the second half section of reference sample B.On the contrary, comparative example G includes the first half section (only containing Pt) of reference sample B and the second half section (only containing Pt) of reference sample C.New comparative " subregion " sample is carried out with as described above to CO and HC Performance Evaluation similar for reference sample A-C.Test result is shown in Fig. 5 and 6 and table 1.
Sample test
By following method, the washcoat catalyst composites of preparation in embodiment 1-3 is tested: first coated monolithic is installed in the waste gas stream of test Diesel engine, and injection (post-injection, PI) is aging after then bringing it about high temperature.This is maintained at 400 DEG C by making the temperature of catalyst front end face and then periodically injects fuel in the waste gas stream before catalyst and complete.The fuel sprayed enters catalyst and burns, thus makes the temperature that catalyst rear end face records increase.The temperature of catalyst rear end face is controlled by controlling the fuel quantity spurted in waste gas stream.In this way, the temperature of catalyst rear end face circulates 25 hours (altogether 50 circulations) with the interval of 15 minutes to profit between 400 DEG C and 700 DEG C.
After aging, utilize Europe light vehicle certification newly to discharge driving cycle (NEDC) and coated monolithic is estimated for the performance of test engine CO and HC.By separately installed for monolithic in the waste gas stream of 3LBMWM57 electromotor (Europe 4 standard), described electromotor outwards discharges the HC of CO and the 0.4g/km of 1.6g/km in NEDC circulates.Along with explanation " startup " electromotor circulated according to NEDC, monitor CO and HC concentration in the front and back of coated monolithic, to calculate the catalyst conversion to CO and HC.After test, as described previously the monolithic of preparation in embodiment A-C is cut in half, to prepare embodiment D-G.In embodiment A-G, the test result of the coated monolithic of preparation is shown in Fig. 5 and 6 and table 1.
As shown in figs. 5 and 6, the Diesel engine engine bench test of subregion sample D-G shows, in 700 DEG C carry out the rear injection of 25 hours aging after, proparea scribbles Pt/Pd catalyst washcoat layer formulation and back zone scribbles compared with the monolithic of the monolithic of only washcoat preparation containing the Pt zone coated contrary with the distribution of complex and noble metal, and the oxidation of CO and HC is significantly better.It is true that utilize this novel washcoat scheme (comparative sample D and F, compared with reference sample C) to obtain state-of-the-art with this area only containing the result that the DOC catalyst of Pt is identical.These results are unexpected, because it has generally been thought that Pt is positioned at during proparea more effective, and in proparea, it is from generally relevant to location, back zone high temperature exothermic.Owing to utilizing this novel partition scheme display Pt/Pd catalyst can obtain the result identical with only catalyst containing Pt, therefore there is the great chance reducing the overall cost of DOC.Additionally, utilize this partition scheme to be particularly useful for eliminating the high levels of CO relevant to advanced combustion engine and HC (particularly methane).Result is summarized in table below.
Although showing described multiple embodiments on standard (Europe 4) Diesel engine, the present invention can use in standard diesel oil and advanced burning diesel oil application.
" embodiment ", " particular ", " one or more embodiment " involved in this specification refers to that invention includes specific nature, structure, material or the characteristic simultaneously described with embodiment.Additionally, the phrase that in this specification, many places occur such as " in one or more embodiment ", " in certain embodiments ", " in one embodiment " do not imply that the embodiment that the present invention is identical.Additionally, specific nature, structure, material or characteristic can be incorporated in one or more embodiment in any suitable manner.
Although according to specific embodiment, invention has been described herein, it will be appreciated that the principle that is intended to be merely illustrative of the present of these embodiments and application.For people in the art ` person it is readily apparent that multiple modification and change can be carried out the method and apparatus of the present invention when without departing from the spirit and scope of the present invention.It is, therefore, intended that the modification that present invention resides in claims and its equivalency range and change.

Claims (14)

1. the oxidation catalyst compound being used for eliminating engine exhaust emission thing, comprise: there is the carrier substrate of certain length, arrival end and the port of export, diesel oxidation catalyst catalysis material on described carrier substrate, including the diesel oxidation catalyst catalysis material in the first washcoat district and the second washcoat district；Described first washcoat district comprises the first washcoat and the first refractory metal oxides load, and described first washcoat contains platinum and the mixture of palladium component, and described first washcoat district is adjacent with the described arrival end of described carrier substrate；And described second washcoat district comprises the second washcoat and the second refractory metal oxides load, described second washcoat contains platinum component, described second washcoat district is adjacent with the described port of export of described carrier substrate, wherein at least the 50% of palladium component total amount is arranged in described first washcoat district, and at least the 50% of platinum component total amount is arranged in described second washcoat district；And wherein the second washcoat is substantially free of palladium.
2. the oxidation catalyst compound of claim 1, wherein said first washcoat district extends to the total length of described base material, and described second washcoat district and described first washcoat district is at least some of overlapping.
3. the oxidation catalyst compound of claim 1, wherein said first washcoat district extends to the 5% to 95% of described length substrate from described arrival end, and described second washcoat district extends to the 5% to 95% of described length substrate from the described port of export.
4. the oxidation catalyst compound of claim 3, wherein said first washcoat district and described second washcoat district are overlapped.
5. the oxidation catalyst compound of claim 1, wherein said platinum and described palladium exist from 1:10 to 4:1 with the ratio of platinum total amount Yu palladium total amount.
6. the oxidation catalyst compound of claim 1, HC and CO oxidation that wherein said catalysis material makes advanced burning diesel oil engine emission effectively, that include methane component, described first washcoat district activation is for making CO and HC aoxidize under relevant maximum discharge and cryogenic conditions running to described advanced burning diesel oil electromotor, and described advanced burning diesel oil electromotor runs by making the temperature of cylinder internal-combustion flame reduces and increase fuel supplies concordance and degree of mixing before lighting a fire.
7. the oxidation catalyst compound of claim 1, one of wherein said first refractory metal oxides load and described second refractory metal oxides load or the two comprise aluminium oxide, silicon dioxide, zirconium oxide, titanium dioxide and its combination in one or more.
8. the oxidation catalyst compound of claim 1, one of wherein said first washcoat and described second washcoat or the two comprise in zeolite, alkaline-earth oxide, rare earth oxide and base metal oxide further one or more.
9. the oxidation catalyst compound of claim 1, comprises the priming coat being substantially free of noble's metal component further, and described priming coat is coated on described carrier substrate below one of described first washcoat district and described second washcoat district or the two.
10. the oxidation catalyst compound of claim 1, wherein said first refractory metal oxides load comprises ceria and the molecular sieve containing zeolite, and described zeolite is selected from beta-zeolite, ZSM-5 or zeolite-Y.
11. the oxidation catalyst compound of claim 1, wherein said catalyst composites has 30g/ft3To 350g/ft3The platinum of scope and the total bearing capacity of palladium.
12. for the method processing diesel exhaust stream, including making conventional diesel waste gas stream or advanced burning diesel oil waste gas stream by catalysis soot filter, described waste gas stream first passes through the oxidation catalyst compound any one of claim 1-11.
13. the method for claim 12, farther include conventional diesel waste gas stream or advanced burning diesel oil waste gas stream are introduced the SCR catalytic article being positioned at described catalysis soot filter downstream.
14. the method for claim 12, CO and HC is made to aoxidize including under the maximum discharge relevant to advanced burning diesel oil electromotor operation and cryogenic conditions.
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